Condensation polymers containing methine ultraviolet radiation-absorbing residues and shaped articles produced therefrom

ABSTRACT

A composition useful for molding into articles such as food containers, soft drink bottles, cured structural plastics and the like, comprising molding grade linear or unsaturated polyester or polycarbonate having reacted or copolymerized therein the residue of one or a mixture of methine reactants of the formula ##STR1## wherein R 1  is hydrogen or an unsubstituted or substituted alkyl, alkenyl, cycloalkyl or aryl radical; 
     A 1  is an unsubstituted or substituted phenylene radical; 
     A 2  is an unsubstituted or substituted 1,4-phenylene radical; 
     R 2  is hydrogen or an unsubstituted or substituted alkyl, cycloalkyl or aryl radical; 
     R 3  is cyano or ##STR2## and R 4  is one of the substituents which R 3  can represent or an unsubstituted or substituted carbamoyl, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, aryl or aromatic heterocyclic radicals. 
     The methine residues are present in the polymer as an integral part of the polymer chain and absorb ultraviolet radiation in the range of about 250 to about 390 nm. The residues are non-extractable from the polymer and stable at the conditions at which the polymers are manufactured and processed.

DESCRIPTION

This invention pertains to novel condensation polymers such aspolyesters and polycarbonates wherein an ultraviolet light screeningamount of one or more methine moieties has been incorporated in thechain or backbone of the polymer. This invention also pertains tocontainers, such as those suitable for packaging beverages and foods,manufactured from our novel condensation polymers.

Many products such as certain fruit juices, soft drinks, wines, foodproducts, cosmetics and shampoos are deleteriously affected, i.e.,degraded, by ultraviolet (UV) light when packaged in plastic containerswhich pass significant portions of the available light at wavelengths inthe range of approximately 250 to 390 nm. It is well known that polymerscan be rendered resistant to degradation by UV light by physicallyblending in such polymers various UV light stabilizers such asbenzophenones, benzotriazoles and resorcinol monobenzoates. See, forexample, Plastics Additives Handbook, Hanser Publishers, Library ofCongress, Catalog No. 83-062289, pp 128-134. Normally, such stabilizersare used in a weight concentration of at least 0.5 percent. Althoughthese stabilizers function well to absorb radiation in the range ofabout 300 to 350 nm, absorbance in the range of 300 to 350 nm is notadequate to protect comestibles subject to UV light degradation packagedin clear plastic, i.e., essentially colorless, transparent plastic. Thestabilizers in the known stabilized polymer compositions can beextracted from the polymer by solvents such as acids, alcohols and thelike present in foods or beverages packaged within the stabilizedpolymers. Furthermore, many compounds used to stabilize polymers are notstable at high temperatures and would decompose under the conditions atwhich polyesters are manufactured or processed. Decomposition of suchstabilizers frequently causes yellow discoloration of the polyester andresults in the polyester containing little, if any, of the stabilizer.

U.S. Pat. No. 4,340,718 discloses the copolymerization of certainmethine stabilizers with polyesters. The patent further discloses thatthe concentration of the methine stabilizers in the polyesters should bein the range of 0.3 to 5.0 percent, preferably 0.6 to 2.0 percent, i.e.,6000 to 20,000 ppm, to impart to the basic polyester improvedweatherability in outdoor applications. This patent discloses neitherthe particular methine compounds utilized in the compositions providedby this invention nor the use of methine compounds in low concentrationsfor the purpose of screening UV light.

U.S. Pat. No. 4,617,374 discloses that polyesters having certain methinecompounds reacted therein to absorb light in the range of 320 to 380 nm.That patent, however, does not disclose the methine compounds used inthe polyester compositions and articles molded therefrom provided by ourinvention.

Our invention concerns a composition comprising molding gradecondensation polymer having copolymerized therein the residue of amethine compound or mixture of methine compounds having the formula:##STR3## wherein R¹ is hydrogen or an unsubstituted or substitutedalkyl, alkenyl, cycloalkyl or aryl radical;

A¹ is an unsubstituted or substituted phenylene radical;

A² is an unsubstituted or substituted 1,4-phenylene radical;

R² is hydrogen or an unsubstituted or substituted alkyl, cycloalkyl oraryl radical;

R³³ is cyano or ##STR4## and R⁴ is one of the substituents which R³ canrepresent or an unsubstituted or substituted carbamoyl, alkanoyl, aroyl,alkylsulfonyl, arylsulfonyl, aryl or aromatic heterocyclic radicals.

Examples of the unsubstituted alkyl groups include methyl, ethyl,propyl, 2-propyl, butyl, 2-butyl, hexyl, octyl, 2-ethylhexyl, decyl,dodecyl, etc. The cycloalkyl groups may be cyclopentyl, cyclohexyl,cycloheptyl and the like. The aryl groups may be, for example,carbocyclic aryl such as phenyl and naphthyl. Examples of theunsubstituted alkanoyl, alkylsulfonyl and arylsulfonyl include acetyl,propionyl, butyryl, pivaloyl, hexanoyl, 2-ethylhexanoyl, methylsulfonyl,ethylsulfonyl, propylsulfonyl, octylsulfonyl, phenylsulfonyl, etc.Pyrolyl, pyridyl, pyrimidyl, 2-benzothiazolyl, 2-benzoxazolyl,2-benzimidazolyl, 2-thienyl, 2-furanyl, 1,3,4-thiadiazol-2-yl,1,2,4-thiadiazol-5-yl and groups having the structure: ##STR5## areexamples of the unsubstituted aromatic heterocyclic residues which mayconstitute a part of the methine compounds. The alkyl radicalsrepresented by R¹ and R² can be substituted with a wide variety ofsubstituents such as alkoxy, alkylthio, halogen, hydroxy, cycloalkyl,cycloalkoxy, alkanoyloxy, cyano, aryl, aryloxy, arylthio, etc. Thecycloalkyl, aryl and aromatic heterocyclic groups can be substitutedwith unsubstituted or substituted alkyl and the various R⁴ substituentsas well as with any of the substituents set forth hereinabove. Normally,those substituents containing alkyl moieties, such as alkyl,hydroxyalkyl, alkoxyalkyl, etc., will not contain more than a total of12 carbon atoms. The unsubstituted and substituted cycloalkyl groupstypically will contain from 5 to 12 carbon atoms whereas theunsubstituted and substituted aryl groups will contain from 6 to 12carbon atoms. Illustrative of the phenylene radicals represented by A¹and A² are groups having the structure: ##STR6## respectively, whereinR⁵ and R⁶ are hydrogen, alkyl, alkoxy, halogen or ##STR7##

The methine compounds which are particularly preferred have the formula:##STR8## wherein R¹ is hydrogen or lower alkyl; R³ is cyano or loweralkoxycarbonyl; and R⁴ is cyano, lower alkoxycarbonyl, carbamoyl, loweralkylsulfonyl, phenylsulfonyl, tolylsulfonyl, phenyl or tolyl, in whichlower designates a carbon content of up to about 4 carbon atoms.

The methine compounds can be prepared using known procedures by reactingan intermediate carbonyl compound II with an active methylene compoundIII under Knovenagel reaction conditions, e.g., ##STR9##

Lower alcohols such as methanol, ethanol and 2-propanol are usuallysuitable solvents. With certain reactants, for example when R³ is nothydrogen, it is sometimes advantageous to conduct the reaction in ahydrocarbon solvent such as benzene or toluene to permit the water to beazeotropically removed as it is formed. Bases such as piperidine,piperidine acetate, pyrrolidine, sodium acetate and pyridine areeffective in promoting the reaction.

Intermediate carbonyl compounds II are prepared according to knownprocedures by reacting α-chlorotoluate esters IV with p-carbonylphenolcompounds V which are known compounds and/or can be obtained bypublished procedures or techniques analogous thereto. ##STR10##

The polyesters which may be used in the preparation of the compositionsof our invention include linear, thermoplastic, crystalline or amorphouspolyesters produced by conventional polymerization techniques from oneor more diols and one or more dicarboxylic acids. The polyestersnormally are molding or fiber grade and have an inherent viscosity (IV)of about 0.4 to about 1.2. The preferred polyesters comprise at leastabout 50 mole percent terephthalic acid residues and at least about 50mole percent ethylene glycol and/or 1,4-cyclohexanedimethanol residues.Particularly preferred polyesters are those containing from about 75 to100 mole percent terephthalic acid residues and from about 75 to 100mole percent ethylene glycol residues.

The unsaturated, curable polyesters which may be used in our novelcompositions are the polyesterification products of one or more glycolsand one or more unsaturated dicarboxylic acids or their anhydrides.Typical of the unsaturated polyesters is the polyesterification productof (a) 1,4-cyclohexanedimethanol and/or 2,2-dimethyl-1,3-propanediol andoptionally an additional dihydric alcohol, such as ethylene glycol, and(b) maleic acid or fumaric acid and an aromatic dicarboxylic acid, whichwhen crosslinked with an ethylenically-unsaturated monomer, e.g.,styrene, produces a cured polyester resin which has, for example, highthermal resistance, high heat distortion values, excellent electricaland mechanical properties, and excellent resistance to chemicals.

Solutions of such unsaturated polyester resins in anethylenically-unsaturated monomer such as styrene commonly are referredto as polyester resins.

The unsaturated polyester resins may be prepared in the presence ofgelation inhibitors such as hydroquinone or the like, which are wellknown in the art of polyesterification. The esterification may becarried out for example under an inert blanket of gas such as nitrogenin a temperature range of 118°-220° C. for a period of about 6-20 hoursuntil an acid number below 100 and preferably below 50 is obtained,based on milliequivalents of KOH necessary to neutralize 1 gram of theunsaturated polyester. The resulting polyester may be subsequentlycopolymerized, cross-linked, or cured with "curing amounts" of any ofthe well-known ethylenically unsaturated monomers used as solvents forthe polyesters. Examples of such monomers include styrene, alpha-methylstyrene, vinyl toluene, divinyl benzene, chlorostyrene, and the like aswell as mixtures thereof. Typically, the mole ratio of such unsaturatedmonomer to the unsaturated moiety (e.g., maleic acid residue) in thepolyester is from about 0.5 to about 3.0, although the "curing amounts"of such monomer can be varied from these ratios.

It is preferred that the unsaturated polyester be prepared from one ormore dihydric alcohols, fumaric or maleic acid or mixtures thereof, andup to about 60 mol percent of total acid component of o-phthalic,isophthalic or terephthalic acids or mixtures thereof. Preferred for thedihydric alcohol component is one or a mixture of propylene glycol,neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, ethylene glycol, ordiethylene glycol. A specific preferred unsaturated polyester isprepared from about 75 to 100 mole percent propylene glycol, and as theacid component, from, about 75 to 100 mole percent o-phthalic and maleicacids in a mole ratio of from about 1/2 to about 2/1. Typical of theseunsaturated polyesters are those disclosed, for example, in U.S. Pat.No. 4,359,570 incorporated herein by reference.

The diol components of the described polyesters may be selected fromethylene glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol,1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol,1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol,1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,X,8-bis(hydroxymethyl)-tricyclo[5.2.1.0]-decane wherein X represents 3,4, or 5; and diols containing one or more oxygen atoms in the chain,e.g., diethylene glycol, triethylamine glycol, dipropylene glycol,tripropylene glycol and the like. In general, these diols contain 22 to18, preferably 2 to 8 carbon atoms. Cycloaliphatic diols can be employedin their cis or trans configuration or as mixtures of both forms.

The acid components (aliphatic, alicyclic, or aromatic dicarboxylicacids) of the linear polyester are selected, for example, fromterephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid,1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipicacid, sebacic acid, 1,12-dodecanedioic acid,2,6-naphthalene-dicarboxylic acid and the like. In the polymerpreparation, it is often preferable to use a functional acid derivativethereof such as the dimethyl, diethyl, or dipropyl ester of thedicarboxylic acid. The anhydrides or acid halides of these acids alsomay be employed where practical.

Typical polycarbonates useful herein are disclosed in Kirk-OthmerEncyclopedia of Chemical Technology, third edition, Volume 18, page479-494, incorporated herein by reference.

The novel polymer compositions provided by this invention are useful inthe manufacture of containers or packages for comestibles such asbeverages and food. By the use of known heat-setting techniques, certainof the polyesters are, in terms of color, I.V. and heat distortion,stable at temperatures up to about 100° C. Such stabilitycharacteristics are referred to herein as "hot-fill" stability. Articlesmolded from these polyesters exhibit good thin-wall rigidity, excellentclarity and good barrier properties with respect to moisture andatmospheric gases, particularly carbon dioxide and oxygen.

The linear polyesters most preferred for use in articles having"hot-fill" stability comprise poly(ethylene terephthalate) andpoly(ethylene terephthalate) wherein up to 5 mole percent of theethylene glycol residues have been replaced with residues derived from1,4-cyclohexanedimethanol, wherein the polyesters have been sufficientlyheat set and oriented by methods well known in the art to give a desireddegree of crystallinity. By definition, a polymer is "hot-fill" stableat a prescribed temperature when less than 2% change in volume of acontainer manufactured therefrom occurs upon filling the same with aliquid at the temperature. For the manufacture of blow-molded beveragebottles, the most preferred polyesters have an I.V. of 0.65 to 0.85, anda Tg of >70° C., and film sections cut from the bottle have a WaterVapor Transmission Rate of 1.5 to 2.5 g mils/100 in.² -24 hrs., a CarbonDioxide Permeability of 20-30 cc. mils/100 in.² -24 hrs.-atm., and anOxygen Permeability of 4-8 cc mils/ 100 in.² -24 hrs.-atom. The Tg isdetermined by Differential Scanning Calorimetry at a scan rate of 20Centigrade Degrees/min., the Oxygen Permeability by the standardoperating procedure of a MOCON OXTRAN 100 instrument of Modern Controls,Inc., of Elk River, Minn., and the Carbon Dioxide Permeability by thestandard operating procedure of a MOCON PERMATRAN C II, also of ModernControls.

The concentration of the residue of the methine compound in thecondensation polymer can be varied substantially depending, for example,on the intended function of the UV-absorbing residue and/or the end usefor which the polymer composition is intended. When the polymercomposition is to be used in the fabrication of relatively thin-walledcontainers to screen UV light in the range of about 250 to 390 nm, theconcentration of the residue of the methine compound normally will be inthe range of about 50 to 1500 ppm (parts by weight per million parts byweight polymer) with the range of about 200 to 800 ppm being especiallypreferred.

When the levels of the present ultra-violet light absorbers areincreased to higher levels such as 5,000 ppm (0.5 weight percent) orhigher, polymers containing these ultra-violet light absorbers showimproved resistance to weathering and when these polymers per se orfibers thereof are dyed with disperse dyes, at a concentration, forexample, of from about 0.01 to about 5.0% based on weight of polymer orfiber, many dyes exhibit increased lightfastness. Such disperse dyes areshown, for example, in U.S. Pat. Nos.: 4,305,719; 2,746,952; 2,746,953;2,757,173; 2,763,668; 2,771,466; 2,773,054; 2,777,863; 2,785,157;2,790,791; 2,798,081; 2,805,218; 2,822,359; 2,827,450; 2,832,761;2,852,504; 2,857,371; 2,865,909; 2,871,231; 3,072,683; 3,079,373;3,079,375; 3,087,773; 3,096,318; 3,096,332; 3,236,843; 3,254,073;3,349,075; 3,380,990; 3,386,990; 3,394,144; 3,804,823; 3,816,388;3,816,392; 3,829,410; 3,917,604; 3,928,311; 3,980,626; 3,998,801;4,039,522; 4,052,379; and 4,140,683, the disclosures of which areincorporated herein by reference.

Polymer compositions containing substantially higher amounts, e.g., fromabout 2.0 to 10.0 weight percent, of the residue of one or more of themethine compounds described herein may be used as polymer concentrates.Such concentrates may be blended with the same of different polymeraccording to conventional procedures to obtain polymer compositionswhich will contain a predetermined amount of the residue or residues ina non-extractable form. In the preparation of these highly loaded,polymer composition concentrates the residue preferably is divalent andthus is derived from a difunctional methine compound such as thecompound of Example 2.

The preparation of the methine compounds and their use in preparing thecompositions of our invention are further illustrated by the followingexamples.

EXAMPLE 1

To a solution of p-methoxycarbonylbenzyl alcohol (332.0 g, 2.0 mol) inmethylene chloride (600 mL) is added thionyl chloride (380 g, 3.2 mol)dropwise over 3 hours and the reaction mixture heated at gentle refluxfor 6 hours, allowing excess gases to escape. The excess thionylchloride and methylene chloride are removed and the yellow oiltriturated with hexane to yield a total of 300 g (81.5% yield) of white,solid methyl α-chloro-p-toluate, the identity of which is confirmed byelemental analysis and mass spectrum analysis as follows:

p-Hydroxybenzaldehyde (39.0 g, 0.32 mol) is dissolved in water (400 mL)containing 15.0 g of sodium hydroxide. To this red solution is addedmethyl α-chloro-p-toluate (66.0 g, 0.36 mol) and the reaction mixture isheated for 5 hours at reflux. After being cooled, the product iscollected by filtration washed with water, and finally recrystallizedfrom methanol and water mixture to yield 48.0 g of product (55.5%yield). Mass spectroscopy analysis confirms the product to be methyl4-[(4-formylphenoxy)methyl]benzoate.

A mixture of methyl 4-[(4-formylphenoxy)methyl]benzoate (1.35 g, 0.005mol), malononitrile (0.33 g, 0.005 mol), methanol (15 mL), andpiperidine (5 drops) is heated at reflux for 1 hour and cooled. Theresulting solid material is collected by filtration, washed withmethanol and dried in air to yield 0.72 g of product which massspectroscopy confirms is the expected methyl4-[[4-(2,2-dicyanovinyl)phenoxy]methyl]benzoate having the structure:##STR11##

This methine compound exhibits an absorption maximum (λmax) in methylenechloride at 349 nm.

EXAMPLE 2

Methyl 4-[(4-formylphenoxy)methyl]benzoate (1.35 g, 0.005 mol) isreacted with methyl cyanoacetate (0.50 g, 0.005 mol) and the essentiallywhite solid isolated according to the procedure described in Example 1to yield 1.57 g (89.7% yield) of product which mass spectroscopyconfirms is methyl4-[[4-(2-methoxycarbonyl-2-cyanovinyl)phenoxy]methyl]benzoate.

EXAMPLE 3

Methyl 4-[(4-formylphenoxy)methyl]benzoate (1.35 g, 0.005 mol) isreacted with methylsulfonylacetonitrile (0.60 g, 0.005 mol) and theproduct is isolated according to the procedure described in Example 1 toobtain 1.16 g (62.7% yield) of the expected product methyl4-[[4-(2-cyano-2-methylsulfonylvinyl)phenoxy]methyl]benzoate having thestructure: ##STR12## which is confirmed by mass spectroscopy analysis.This methine compound has an absorption maximum at 337 nm in methylenechloride.

Additional examples of methine compounds which may be used in thepreparation of the novel polymer compositions provided by our inventionare set forth in Table 1. These compounds may be prepared according tothe procedures described in the preceding examples or by similar meansand conform to formula: ##STR13##

    __________________________________________________________________________     Ex.                                                                                              R.sup.5                                                                             R.sup.6                                                                              R.sup.2                                                                            R.sup.3   R.sup.4                       __________________________________________________________________________    4  4-COOCH.sub.3   H     H      H    CN        CONH.sub.2                     5  4-COOCH.sub.3   H     H      H    CN        CONHCH.sub.3                   6  4-COOCH.sub.2 CH.sub.2 OH                                                                     H     H      H    CN        CONHCH.sub.2 CH.sub.2 OH       7  4-COOCH.sub.3   H     H      H    CN        CONHCH.sub.2 CH.sub.2 OH       8  3-COOCH.sub.3   H     H      H    CN        CONHC.sub.6 H.sub.5            9  2-COOCH.sub.3   H     H      H    CN        CON(CH.sub.3)C.sub.6                                                          H.sub.5                        10 4-COOCH.sub.3   H     H      H    CN        SO.sub.2 C.sub.6 H.sub.5       11 4-COOCH.sub.3   H     H      H    CN        CONHC.sub.6 H.sub.5            12 4-COOC.sub.2 H.sub.5                                                                          H     H      H    COOC.sub.2 H.sub.5                                                                      COOC.sub.2 H.sub.5             13 4-COOH          H     H      H    CN        COOCH.sub.3                    14 4-COOCH(CH.sub.3).sub.2                                                                       H     H      H    CN        C.sub.6 H.sub.5                15 4-COOCH.sub.3   H     H      H    CN        COC(CH.sub.3 ).sub.3           16 4-COOCH.sub.3   H     H      H    CN                                                                                       ##STR14##                     17 4-COOCH.sub.2 C.sub.6 H.sub.5                                                                 H     H      H    CN                                                                                       ##STR15##                     18 3-COOCH.sub.2 OC.sub.6 H.sub.5                                                                H     H      H    CN                                                                                       ##STR16##                     19 3-COOC.sub.6 H.sub.5                                                                          H     H      H    CN                                                                                       ##STR17##                     20 3-COOC.sub.6 H.sub.11                                                                         H     H      H    CN                                                                                       ##STR18##                     21 3-COOCH.sub.2 C.sub.6 H.sub.11                                                                H     H      H    CN                                                                                       ##STR19##                     22                                                                                ##STR20##      H     H      H    CN                                                                                       ##STR21##                     23 2-COOCH.sub.2 CH.sub.2 OH                                                                     H     H      H    COOC.sub.2 H.sub.5                                                                       ##STR22##                     24 2-COOCH.sub.2 CH.sub.2 OCH.sub.3                                                              H     H      H    CN        C.sub.6 H.sub.4 4-CH.sub.3                                                    1                              25 4-COOCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                                       H     H      H    CN        C.sub.6 H.sub.4 3-Cl           26 4-COOCH.sub.2 CH.sub.2 CN                                                                     H     H      H    CN        SO.sub.2 (CH.sub.2).sub.4                                                     H                              27 4-COOCH.sub.2 CH.sub.2 Cl                                                                     H     H      H    CN        SO.sub.2 C.sub.6 H.sub.3                                                      3,4-di-Cl                      28 4-COOC.sub.6 H.sub.4 4-CH.sub.3                                                               H     H      H    CN        COC.sub.6 H.sub.5              29 4-COOCH.sub.2 CH.sub.2 CH.sub.3                                                               H     H      H    CN        COC.sub.6 H.sub.4 4-OCH.sub                                                   .3                             30 4-COOCH.sub.2 CH.sub.2 NHCOCH.sub.3                                                           H     H      H    CN        COC.sub.6 H.sub.4 2-OCH.sub                                                   .3                             31 4-COOCH.sub.2 C.sub.6 H.sub.10 4-CH.sub.2 OH                                                  H     H      H    CN        COC.sub.6 H.sub.4 3-OCH.sub                                                   .3                             32 4-COOCH.sub.2 CHCH.sub.2                                                                      H     H      H    CN        COOCH.sub.2 CH.sub.2 OH        33 4-COO(CH.sub.2 CH.sub.2 O).sub.2 H                                                            H     H      H    CN        COOC.sub.6 H.sub.5             34 4-COOC.sub.6 H.sub.5                                                                          H     H      H    COOCH.sub.3                                                                             COOCH.sub.3                    35 4-COOCH.sub.2 CH.sub.2 OOCCH.sub.3                                                            H     H      H    COOC.sub.6 H.sub.5                                                                      COOC.sub.6 H.sub.5             36 4-COOCH.sub.3   H     H      CH.sub.3                                                                           CN        COOCH.sub.3                    37 4-COOCH.sub.3   H     H      C.sub.6 H.sub.5                                                                    CN        COOC.sub.2 H.sub.5             38 4-COOCH.sub.3   H     H      C.sub.6 H.sub.11                                                                   CN        CN                             39 4-COOH          2-OCH.sub.3                                                                         H      H    CN        CON(CH.sub.3).sub.2            40 2-COOCH.sub.3   5-COOCH.sub.3                                                                       H      H    CN        CN                             41 3-COOCH.sub.3   4-COOCH.sub.3                                                                       H      H    CN        CONH.sub.2                     42 3-COOH          5-COOH                                                                              H      H    CN        SO.sub.2 C.sub.6 H.sub.5       43 4-COOCH.sub.3   2-Cl  H      H    CN        CONHC.sub.6 H.sub.4                                                           2-OCH.sub.3                    44 2-COOCH.sub.3   4-Br  H      H    CN        CN                             45 4-COOCH.sub.3   2-CH.sub.3                                                                          H      H    CN                                                                                       ##STR23##                     46 4-COOCH.sub.3   H     3-CH.sub.3                                                                           H    CN        CN                             47 4-COOCH.sub.3   H     3,5-di-CH.sub.3                                                                      H    CN                                                                                       ##STR24##                     48 4-COOCH.sub.3   H     2-OCH.sub.3                                                                          H    CN        CN                             49 4-COOCH.sub.3   H     2-OCH.sub.3                                                                          H    CN        COOCH.sub.3                    50 4-COOCH.sub.3   H     2,6-di-OCH.sub.3                                                                     H    CN        COOCH.sub.2 CH.sub.2 OH        51 4-COOCH.sub.3   H     3-Cl   H    CN        COOCH.sub.2 OC.sub.6                                                          H.sub.5                        52 4-COOCH.sub.3   H     3-Br   H    CN        COOCH.sub.2 CH.sub.2                                                          OCH.sub.3                      53 4-COOCH.sub.3   H     2-OC.sub.2 H.sub.5                                                                   H    CN        COOC.sub.6 H.sub.11            54 4-COOCH.sub.3   H     2-OCH.sub.3                                                                          H    COOCH.sub.3                                                                             COOCH.sub.3                    55 3-COOCH.sub.3   H     2-OCH.sub.3                                                                          H    COOCH.sub.2 CH.sub.2 OH                                                                 COOCH.sub.2 CH.sub.2 OH        56 3-COOCH.sub.3   H     2-OCH.sub.3                                                                          H    COOC.sub.2 H.sub.5                                                                       ##STR25##                     57 2-COOCH.sub.3   H     2-OCH.sub.3                                                                          H    CN                                                                                       ##STR26##                     58 4-COOCH.sub.3   H     2-OCH.sub.3                                                                          H    CN                                                                                       ##STR27##                     59 4-COOCH.sub.3   H     2-OCH.sub.3                                                                          H    CN        COOCH.sub.2 CHCH.sub.2         60 4-COOCH.sub.3   H     2-OCH.sub.3                                                                          H    CN        SO.sub.2 C.sub.6 H.sub.4                                                      4-CH.sub. 3                    61 4-COOCH.sub.3   H     2-OCH.sub.3                                                                          H    CN        CON(CH.sub.2 CH.sub.2                                                         OH).sub.2                      62 4-COOCH.sub.3   H     2-OCH.sub.3                                                                          H    CN        COOH                           63 4-COOH          H     2-OCH.sub.3                                                                          H    CN        COOH                           64 4-COOCH.sub.3   H     2-OCH.sub.3                                                                          H    CN        CONHC.sub.6 H.sub.11           __________________________________________________________________________

EXAMPLE 65

The following materials are placed in a 500-mL, three-necked,round-bottom flask:

97 g (0.5 mol) dimethyl terephthalate

62 g (1.0 mol) ethylene glycol

0.00192 g Ti from a n-butanol solution of acetyl-triisopropyl titanate

0.0053 g Mn from an ethylene glycol solution of manganese acetate

0.0345 g antimony oxide

0.0072 g Co from an ethylene glycol solution of cobaltous acetate

The flask is equipped with a nitrogen inlet, stirrer, vacuum outlet, andcondensing flask. The flask and contents are heated in 200° C. in aBelmont metal bath for 60 minutes and at 210° C. for 75 minutes with anitrogen sweep over the reaction mixture. Then 1.57 mL of an ethyleneglycol slurry of a mixed phosphorus ester composition (Zonyl A) whichcontains 0.012 g phosphorus is added. The temperature of the bath isincreased to 230° C. At 230° C. methyl4-[[4-(2-methoxycarbonyl-2-cyanovinyl)phenoxy]methyl]benzoate (0.0384 g)prepared in Example 2 is added to the flask. Five minutes after thisaddition, a vacuum with a slow stream of nitrogen bleeding in the systemis applied over a five-minute period until the pressure is reduced to200 mm Hg. The flask and contents are heated at 230° C. under a pressureof 200 mm Hg for 25 minutes. The metal bath temperature is increased to270° C. At 270° C. the pressure is reduced slowly to 100 mm Hg. Theflask and contents are heated at 270° C. under a pressure of 100 mm Hgfor 30 minutes. The metal bath temperature is increased to 285° C. andthe pressure is reduced slowly to 4.5 mm Hg. The flask and contents areheated 285° C. under pressure of 4.5 mm Hg for 25 minutes. Then thepressure is reduced to 0.25 mm Hg and polycondensation is continued for40 minutes. The flask is removed from the metal bath and is allowed tocool in a nitrogen atmosphere while the polymer crystallizes. Theresulting polymer has an inherent viscosity of 0.61 measured in a 60/40ratio by weight of phenol/tetrachloroethane at a concentration of 0.5 gper 100 mL. An amorphous 13-mil thick film molded from this polymer tosimulate the sidewall of a container transmits less than 10% light from250 to 370 nm whereas a 13-mil film prepared from a like polyesterwithout the absorber transmits less than 10% light at all wavelengthsabove 320 nm.

EXAMPLE 66

The procedure described in Example 65 is repeated using 0.0384 g (440ppm) of methyl 4-[[4-(2,2-dicyanovinyl)phenoxy]methyl]benzoate fromExample 1 instead of the methine compound used in Example 65. Theresulting polymer is white and has an inherent viscosity of 0.52. Anamorphous 14-mil thick film molded from this polymer transmits less than10% light from 250 to 363 nm whereas 14-mil film prepared from a likepolyester without the copolymerized absorber transmits less than 10%light from 250 to only 320 nm.

EXAMPLE 67

The procedure described in Example 65 is repeated using 0.0384 g (400ppm) methyl 4[[4-(2-cyano-2-methylsulfonylvinyl)phenoxy]methyl]benzoateobtained in Example 3 instead of the methine compound used in Example 3instead of the methine compound used in Example 65. The resultingpolymer has an inherent viscosity of 0.60 measured in a 60/40 ratio byweight of phenol/tetrachloroethane at a concentration of 0.5 g per 100mL. An amorphous 14-mil thick film molded from this polymer to simulatethe sidewall of a container transmits less than 10% light from 250-351nm whereas a 14-mil thick film prepared from a like polyester withoutthe absorber transmits less than 10% light at all wavelengths above 320nm.

EXAMPLE 68

Example 65 is repeated using 0.0384 g of methyl4-[[4-2-carbamoyl-2-cyanovinyl)phenoxy]methyl]benzoate from Example 4instead of the UV absorbing methine compound used in Example 65. Theresulting polymer has an inherent viscosity of 0.53 measured in a 60/40ratio by weight of phenol/tetrachloroethane at a concentration of 0.5 gper 100 mL. An amorphous 14.5-mil thick film molded from this polymerexhibits a strong absorption peak with a maximum at 340 nm.

EXAMPLE 69

Example 65 is repeated using 0.0384 g ofN-(2-hydroxyethyl)-3-[4-[4-(methoxycarbonyl)benzyloxy]phenyl-2-cyano-2-propenamideinstead of the absorber used in Example 65. The resulting polymer has aninherent viscosity of 0.58 measured in a 60/40 ratio by weight ofphenol/tetrachloroethane at a concentration of 0.5 g per 100 mL. Anamorphous 14.5-mil thick film molded from this polymer shows a strongabsorption peak with a maximum at 340 nm.

EXAMPLE 70

Example 65 is repeated using 0.0384 g of3-[4-[4-(methoxycarbonyl)benzyloxy]phenyl]-2-cyano-N-phenyl-2-propenamidefrom Example 11 instead of the methine compound used in Example 65. Theresulting polymer has an inherent viscosity of 0.59 measured asdescribed in the preceeding examples. An amorphous 13-mil thick filmmolded from this polyester shows a strong absorption peak with a maximumat 350 nm.

EXAMPLE 71

Example 65 is repeated using 0.0384 g of methyl4-[[4-[2-(1,1-dimethylethoxycarbonyl)-2-cyano-vinyl]phenoxy]methylbenzoatefrom Example 15 instead of the methine compound used in Example 65. Theresulting polymer has an inherent viscosity of 0.54 measured asdescribed in the preceeding examples. As amorphous 15-mil thick filmmolded from this polymer exhibits a strong absorption peak with amaximum at 347 nm.

The inherent viscosities (I.V. of the copolyesters described herein aredetermined according to ASTM D2857-70 procedure in a Wagner Viscometerof Lab Glass Inc., of Vineland, N.J., having a 1/2 mL capillary bulb,using a polymer concentration of 0.5%, by weight, in 60/40, by weight,phenol/tetrachloroethane solvent. The procedure comprises heating thepolymer/solvent system at 120° C. for 15 minutes to enhance dissolutionof the polymer, cooling the solution to 25° C. and measuring the time offlow at 25° C. The I.V. is calculated from the equation: ##EQU1##wherein: {η}=Inherent viscosity at 25° C. at a polymer concentration of0.5 g/100 mL of solvent;

ln=Natural logarithm;

t_(s) =Sample flow time;

t_(o) =Solvent-blank flow time; and

C=Concentration of polymer in grams per 100 mL of solvent=0.50

The nonextractabilities of the methine residues described herein aredetermined as follows:

All extractions ae done in glass containers with distilled solventsunder the time and temperature conditions described below. The sampleform is 1/2-inch×21/2-inch segments cut from the cylindrical side wallportion of 2-liter bottles. All samples are washed with cold solvent toremove surface contaminants and are exposed using 200 mL solvent 100in.² surface area (2 mL/in.²).

Solvent blanks are run under the same extraction conditions withoutpolymer. In most cases samples were extracted, spiked, with a knownamount of additive as a control, and analyzed in duplicates. Thesolvents employed and the extraction conditions for each solvent are:

1. Water. The samples at room temperature are added to solvent andheated at 250° F. for 2 hours. Half of the samples are then analyzed andthe remainder are placed in a 120° F. oven for 30 days.

2. 50% Ethanol/water. The samples at room temperature are added to thesolvent at room temperature, placed in an oven at 120° F. and analyzedafter 24 hours. Another set of samples is aged for 30 days at 120° F.and then analyzed.

3. Heptane. The samples at room temperature are added to solvent at roomtemperature and heated at 150° F. for 2 hours. Part of the samples arecooled to room temperature and analyzed spectrophotometrically and theremainder are allowed to age at 120° F. for 30 days before analysis.

Any suitable analytical technique and apparatus may be employed todetermine the amount of methine residue extracted from the polymer.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. A composition comprising molding grade condensation polymerhaving copolymerized therein a residue of a methine compound or mixtureof methine compounds having the formula: ##STR28## wherein R¹ ishydrogen or an unsubstituted or substituted alkyl, alkenyl, cycloalkylor aryl radical;A¹ is an unsubstituted or substituted phenylene radical;A² is an unsubstituted or substituted 1,4-phenylene radical; R² ishydrogen or an unsubstituted or substituted alkyl, cycloalkyl or arylradical; R³ is cyano or ##STR29## and R⁴ is one of the substituentswhich R³ can represent or an unsubstituted or substituted carbamoyl,alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, aryl or aromaticheterocyclic radicals.
 2. A composition according to claim 1 wherein thepolymer is a linear polyester having copolymerized therein a total offrom about 200 to 800 ppm or the residue of the methine compound or themixture of methine compounds.
 3. The composition of claim 2 wherein themethine compound has the formula: ##STR30## wherein R¹ is hydrogen oralkyl;R³ is cyano or ##STR31## R⁴ is one of the substituents which R³can represent or carbamoyl, alkanoyl, alkylsulfonyl, arylsulfonyl,phenyl or tolyl; and R⁵ and R⁶ each independently is hydrogen, alkyl,alkoxy, halogen or ##STR32##
 4. A composition of claim 2 wherein themethine compound has the formula ##STR33## wherein R¹ is hydrogen orlower akyl; andR⁴ is cyano, lower alkoxycarbonyl, carbamoyl,N-hydroxyalkylcarbamoyl, N-phenylcarbamoyl, lower alkylsulfonyl,phenylsulfonyl, tolylsulfonyl, phenyl or tolyl.
 5. The composition ofany of claims 1-4 wherein the polyester acid moiety is comprised of atleast about 50 mol % terephthalic acid residue, and the glycol moiety atleast about 50 mol % ethylene glycol or 1,4-cyclohexanedimethanolresidue.
 6. The composition of any of claims 1-4 wherein the polyesteris comprised of from about 75 to 100 mol % terephthalic acid residue andfrom about 75 to 100 mol % ethylene glycol residue.
 7. The compositionof claim 1 wherein the polymer is unsaturated polyester having an acidmoiety comprised of fumaric or maleic acid or mixtures thereof and up toabout 60 mol % of one or a mixture of o-phthalic, isophthalic, orterephthalic acids, and having a glycol moiety comprised of one or amixture of propylene glycol, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, ethylene glycol or diethylene glycol.8. The composition of claim 7 wherein the acid moiety is comprised offrom about 75 to 100 mol % o-phthalic acid and maleic acid in a moleratio of from about 1/2 to about 2/1, and the glycol moiety is comprisedof from about 75 to 100 mol % propylene glycol.
 9. A fiber of thecomposition of claim 1 dyed with from about 0.01 to about 5.0% by weightbased on weight of fiber of a disperse dye.
 10. A formed article of thecomposition of claim
 1. 11. A formed article of the composition of claim4.